Crystallization kinetics and crystalline morphology of poly(ε‐caprolactone) in blends with grafted rubber particles

l’Abee, Roy; Duin, Martin van; Goossens, Jgp Han

doi:10.1002/polb.22025

Cited by 15 publications

(10 citation statements)

References 46 publications

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“…Reducing the grafting density is reducing the nucleation efficiency further. This result is in line with the result of L’Abee et al [24], who showed that in a rubber particle-filled PCL based system, the nucleation efficiency depended on grafting density. For the PCL80 matrix the behaviour is different.…”

Section: Resultssupporting

confidence: 92%

“…The effect was larger in samples with a higher grafting density and shorter grafts as compared to samples with a low grafting density and longer grafts. L’Abee et al [24] showed that, during the in situ preparation of rubber particle-filled PCL, the peroxide used to cross-link the rubber network also caused grafting of PCL chains onto the rubber particles. Transmission electron microscopy (TEM) images of the grafted particles revealed lamellae growing from the surface of the particles, while also an increase in nucleation efficiency was observed which was shown to depend on grafting density [24].…”

Section: Introductionmentioning

confidence: 99%

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The Influence of Graft Length and Density on Dispersion, Crystallisation and Rheology of Poly(ε-caprolactone)/Silica Nanocomposites

et al. 2019

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Different techniques of grafting polymer chains to filler surfaces are often employed to compatibilise filler and polymer matrices. In this paper the influence of graft length and graft density on the state of dispersion, crystallisation and rheological properties of poly(ε-caprolactone) (PCL)/silica (SiO2) nanocomposites are reported. Grafted silica nanoparticles were prepared through polymerisation of PCL from the nanoparticle surface. Graft length was controlled by the reaction time, while the grafting density was controlled by the monomer-to-initiator ratio. Grafted nanoparticles were mixed with PCL of different molecular weights and the state of dispersion was assessed. Different matrix-to-graft molecular weight ratios resulted in different states of dispersion. Composites based on the higher molecular weight matrix exhibited small spherical agglomerates while the lower molecular weight matrix revealed more sheet-like microstructures. The state of dispersion was found to be relatively independent of graft length and density. Under quiescent conditions the grafts showed increased nucleation ability in the higher molecular weight PCL, while in the lower molecular weight matrix the effect was less pronounced. Rheological experiments showed an increase in viscosity with increased filler content, which was beneficial for the formation of oriented structures in shear-induced crystallisation.

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Section: Resultssupporting

confidence: 92%

Section: Introductionmentioning

confidence: 99%

The Influence of Graft Length and Density on Dispersion, Crystallisation and Rheology of Poly(ε-caprolactone)/Silica Nanocomposites

et al. 2019

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“…The Avrami exponent n of the neat PCL shows the value 2.7 suggesting a three‐dimensional growth, in compliance with other authors . The n values evaluated from the high‐ and low‐temperature exotherms (a and b in Table ) of the nanocomposites are around 2 indicating possible change in the growth mechanism from the three‐ to two‐dimensional.…”

Section: Resultssupporting

confidence: 87%

Epoxy/poly(ɛ‐caprolactone) nanocomposites: Effect of transformations of structure on crystallization

Kratochvíl

Rotrekl

Kaprálková

et al. 2013

J of Applied Polymer Sci

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The influence of morphology of the epoxy/poly(E-caprolactone) (PCL) system and corresponding nanocomposites with organophilized layered silicate on PCL crystallization was studied by differential scanning calorimetry, scanning, and transmission electron microscopy. The results obtained indicate a significant affecting of nonisothermal PCL crystallization by phase morphology brought about by the reaction-induced phase separation (RIPS) influenced either by various nanoclay contents or the epoxy/PCL ratio. Dispersed morphology of PCL matrix with epoxy globules induces crystallization at higher temperatures. The inverse dispersed morphology of epoxy matrix with PCL inclusions causes crystallization at lower temperature. The co-continuous morphology induces crystallization in both steps. Rate of the second crystallization step is substantially higher than that in the first step. No nucleation effect has been found in the nanocomposites with the added nanofiller. Multicomponent samples show retarded crystallization, i.e., lower crystallinities and lower overall crystallization rate compared with neat PCL. The results obtained suggest that it is primarily morphological/interfacial effects that play a decisive role in the crystallization behavior of PCL in the epoxy/PCL/clay system.

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“…In order to control crystallinity, an understanding of crystallization kinetics is important. The kinetics of crystallization of PCL and some of its blends [10,11,12,13] have been studied previously using differential scanning calorimetry (DSC), employing samples with masses of a few milligrams. However, during the processing of polymers, they are cooled at high rates and their crystallization occurs at a high supercooling.…”

Section: Introductionmentioning

confidence: 99%

Influence of the Cross-Link Density on the Rate of Crystallization of Poly(ε-Caprolactone)

et al. 2018

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Cross-linked poly(ε-caprolactone) (PCL) is a smart biocompatible polymer exhibiting two-way shape memory effect. PCL samples with different cross-link density were synthesized by heating the polymer with various amounts of radical initiator benzoyl peroxide (BPO). Non-isothermal crystallization kinetics was characterized by means of conventional differential scanning calorimetry (DSC) and fast scanning calorimetry (FSC). The latter technique was used to obtain the dependence of the degree of crystallinity on the preceding cooling rate by following the enthalpies of melting for each sample. It is shown that the cooling rate required to keep the cooled sample amorphous decreases with increasing cross-link density, i.e., crystallization process slows down monotonically. Covalent bonds between polymer chains impede the crystallization process. Consequently, FSC can be used as a rather quick and low sample consuming method to estimate the degree of cross-linking of PCL samples.

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Crystallization kinetics and crystalline morphology of poly(ε‐caprolactone) in blends with grafted rubber particles

Cited by 15 publications

References 46 publications

The Influence of Graft Length and Density on Dispersion, Crystallisation and Rheology of Poly(ε-caprolactone)/Silica Nanocomposites

The Influence of Graft Length and Density on Dispersion, Crystallisation and Rheology of Poly(ε-caprolactone)/Silica Nanocomposites

Epoxy/poly(ɛ‐caprolactone) nanocomposites: Effect of transformations of structure on crystallization

Influence of the Cross-Link Density on the Rate of Crystallization of Poly(ε-Caprolactone)

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